Lubricating oil



Patented Jan. 1, 1952 7 2,581,132 LUBRICATING on.

Roy F. Nelson, Alton J. Deutser, and Melvin R. Hefty, Port Arthur, Tex., assignors to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application July 13, 1949,

Serial No; 104,598

24 Claims. 1

This invention relates to a lubricating composition adapted to form a Water-in-oil emulsion in the presence of water, and particularly to such a composition adapted to lubricate'reciprocating steam engines of marine vessels and-known as a marine engine oil. a 1

For many years, marine engine oils have been compounded with about 10-20% or more by weight of blown rapeseed oil in mineral lubricating oil. The basic function of the blown rapee seed oil is generally considered to be as an-emulsifier, although it imparts other properties to the lubricant compositionwhich are both desirable and undesirable. Recently, due to a critical shortage of rapeseed oil as well as other equivalent fatty materials, with resultant increase in selling price and doubt concerning future availability, efforts have been made to develop the use of synthetic surface active materials, for the blown rapeseed oil. Since there is considerable water drip from the steam cylinders over the moving parts of marine engines, it is desirable that a lubricant of this type be capable to taking up a considerable amountof water. It is very important that this water be taken up in the form of a water-in-oil emulsion wherein the oil is in the continuous phase in order that the mixture will have good lubricating properties. In addition to this requirement of forming an emulsion of the proper water-in-oil type in the presence of water, the lubricant should also emulsify easily or readily under the mechanical mixing action of the moving parts of the engine such as the eccentrics, links, crosshead guides and slipper combs, and should also have satisfac tory emulsion stability-to resist separation of oil and water from the formed emulsion under the tion is a mineral lubricating oil of any known and available type, either from parafiin base or naphthene base crudes, or from mixed base crudes. Theviscosity of the mineral lubricating oil can vary throughout the lubricating oil viscosity range depending on the particular service conditions under which it is to be used, although for most marine engine oil service the viscosity at 100 F. (Saybolt Universal) may vary between about 400 and 1500 seconds. From the standpoint of providing a readily available and economical lubricating base, a naphthene base lubricating oil which has been prepared by light acid treating, neutralizing, steaming and brightening, and which has a Saybolt Universal viscosity at 100 F. of about 500-1200 seconds, is preferred. As pointed out above, the mineral lubricating oil constitutes at least by weight of the com position, preferably about or more thereof.

In accordance with the present invention, this lubricating base is compounded with about 0.05-0.4% by weight based on the composition of a substituted glyoxalidine having the formula atoms, and X is a group selected from hydroxyalkyl, amino-alkyl and amino-alkylene-iminoalkyl wherein the said alkyl radical of each elevated temperature'conditions encountered in the lubrication of the engine. desired include satisfactory adherence to the parts to be lubricated, satisfactory feeding of the lubricant through the customary wicks to Other properties the engine parts, proper viscosity of the lubricant per 'se and satisfactory emulsion consistency when the lubricant is emulsified with'water. One of the principal objects of the present invention is to provide a satisfactory lubricating composition of this character which forms a water-in-oil emulsion in the presence of water, and which is composed of at least about 90% by weight of mineral lubricating oil containing a small amount of available and highly effective emulsifier additive, or combination of emulsifier additives. "Another object of the present invention is to provide a marine engine oil of this type, which is highly satisfactory in service, and economical in manufacture and use, and whichobviates the need for blown rapeseed oil in the composition.

Other objects andadvantages of the present invention will be apparent from the following description and the appended claims. I The lubricating base oi the present compostoxalidine; alidine; 45

group is lower alkyl. The preparation of compounds of this type by the reaction of a suitable soap-forming fatty acid with an alkylene polyamine is well known as described in Wilson Pattent No. 2,267,965. Examples of suitable compounds of this type for purposes of the present invention are l-amino ethyl 2-undecyl glyoxalidine; l-amino ethyl Z-heptadecenyl glyl-amino ethyl Z-heptadecyl glyoxl-hydroxy ethyl Z-heptadecenyl glyoxalidine; l-amino ethyl ethyl-imino 2-heptadecenyl glyoxalidine; and l-amino isopropyl 2- heptadecenyl 5-methyl glyoxalidine. A very satisfactory material of this character which is com mercially available is l-hydroxy ethyl 2-heptadecenyl glyoxalidine which is manufactured by Carbide and Carbon Chemicals Company under the name Cationic Amine-220.

It has been discovered that, while a very large number of other known surface activeagents tested were either incapable of forming a waterin-oil emulsion, as determined by the electrical conductivity of the emulsion, or required a high proportion in excess of 13% by weight to form a proper type of emulsion, the substituted glyoxalidines of the type described above were outlubricating composition having the required emulsion characteristics in the very low proportion range below 0.4% by weight. This is all the more unexpected since the prior art (of. Wilkes 2,214,152) taught that these substituted glyoxalidines in a proportion above 0.5% by weight in a mineral lubricating oil produced a soluble oil type of composition capable of dispersing as an oil-in-water emulsion. In the following description, the compound l-hydroxy ethyl 2-heptadecenyl glyoxalidine will be discussed by way of example as representative of the effective are suitable for purposes of the present invention. In order to evaluate the effectiveness of the emulsifier additives with respect to emulsion formation and emulsion stability, the following Emulsion Test was employed as described in Federal Specification VVL791d Method 320.1.5. 40

class of substituted glyoxalidines, any one of V which can form the primary additive or emulsifier of the present composition.

While a satisfactory emulsifiable lubricant for certainpurposes can be formed by compounding the substituted glyoxalidine in the small amount listed above in the mineral lubricating oil as the sole additive, it has been found that such composition can be further improved, particularly with respect to emulsion stability, by the addition of a second additive of a. clifierent type and which has a synergistic effect in the presence of the substituted glyoiialidine. Thus, in accordance with the present invention, there is also preferably incorporated .in the composition about 0.1-1.0% by weight of .a fatty acid partial ester of a hexahydric alcoholsa'nhydride, wherein the fatty acid radical of said ester has from 10 to 30 carbon atoms. Thevarious hexahydric alcohols, such as sorbitol, mannitol, dulcitol, and the like, are partially dehydrated and then esterified with soap-forming fatty acids, either saturated or unsaturated, to produce in well known manner compounds suitable for purposes of the present invention. The method of preparation of such comcompounds is described in Brown Patent No. 2,322,820. Specific examples of these compounds are sorbitan mono-oleate, sorbitan mono-laurate, mannitan distearate and clulcitan trilaurate. A very satisfactory material of this type which is commercially available is sorbitan mono-oleate manufactured by Atlas Powder Company under the name Span 80. In the following descripmilliliters of the mineral lubricating oil composition containing the additive or combination of additives were poured together with an equal quantity of water into a 100 ml. graduated cylinder. This cylinder was placed in a water bath maintained at 180 F. and allowed to stand until the contents reached the bath temperature. Then a copper plate stirring paddle (4% long, wide and thick) was lowered into the cylinder until its end was in position about from the bottom of the cylinder. The mixed oil composition and water were then stirred by the paddle driven at 1500 R. P. M. by an electric motor for a 5-minute period, after which the paddle was removed. The graduate with the emulsified contents was kept in the bath for minutes. The graduate was then removed and readings taken of the milliliters of oil separated, the milliliters of water separated and the milliliters of emulsion still present. This test was performed on each sample both with distilled water and with a 1% salt (NaCl) solution. In addition, each graduate following the 60- n. readings was allowed to stand for a further period of 16 hours at atmospheric temperature, and similar readings were again taken to indicate emulsion stability.

The following Table I sets forth the results obtained in this Emulsion Test, utilizing a naphthene base mineral lubricating oil having a Saybolt Universal viscosity at F. of 515 seconds containing the specified amounts of additives A and B, where A is 1-hydroxy ethyl Z-heptadecenyl l'yoxalidine and B is sorbitan mono-oleate. In the table, the three readings in each column for each sample under Emulsion Test signify from left to right the milliliters of oil separated, the milliliters of water separated and the milliliters of emulsion remaining.

TABLE I Naphihene base mineral lubricating oil-SUS at 1 Additive A-l-hydroxy ethyl 2-heptadecenyl glyoxalidine. l Additive B-Sorbitan men-cleats. Conventional 20% blown rapeseed oil comp.

tion, sorbitan mono-oleate is listed by way of example as representative of these various partial esters of hexahydrlc alcohol anhydrides which Sample 16 of the foregoing table was a conventional marine engine oil as previously em- 7 ployed, andconsisted of a 'naphthene base lubricating' oil containing about by weight of blown rapeseed oil. As shown, this conventional marine engine oil composition possessed good emulsion characteristics as illustrated by the 60- minute test with distilled water reported as T-0-80, which signifies only a trace of oil separated, no water separated and 80 milliliters of emulsion still remaining. The similar test in the presence of the salt solution also indicates substantially complete emulsification, with only 1 ml. of oil separated, no water separated and 79 mls. -of emulsion remaining. Likewise, the stability of the emulsion is good as shown by the results reported under the 16-hour columns.

Sample 1 of the table shows that the substituted glyoxalidine alone in a very low concentration effects substantially complete emulsification; however, the stability of the emulsion on standing is somewhat poorer with respect to oil separation. Samples 2 and 3 show that a high h proportion of the, order of about 3% by weight of the sorbitan mono-oleate is required to provide effective emulsification, although this material givesimproved stability against oil separation: Samples. 4. 15 inclusive show that improved results with respect to both emulsion formation and emulsion stability are secured on an average basis by thecombination of from 0.1 to 0.3% by weight of the glyoxalidine additive .with 0.1 to 1.0% by. weight of the sorbitan monooleate, although the results by this particular test for emulsion stability did not quite equal those of the. conventional blown rapeseed oil composition. However, a lubricant composition consisting of the lubricating base with the listed proportions of these two additives constitutes a satisfactory emulsifiable lubricating material for certain purposes, and the total additive concentration is much less than in the conventional blown rapeseed composition.

In addition to forming a tight emulsion of the water-in-oil type which'is stable against separation on standing, it is desirable that the composition easily and rapidly 'form such an emulsion under conditions encountered in marine engine lubrication. A test for evaluating this characteristic will now be described. The apparatus employe'd wasthe same as that described above in connection with the Emulsion Test at 180 F. However, in this case the mixture of 40 ml. of distilled Water and 40 ml. of the composition under test-were maintained at a temperature of and intermittent stirring periods of 30 seconds on and 60 seconds oil were employed. This intermittent stirring was continued until complete emulsification had been attained, that is, when the mixture changed from a thin curdy non-homogeneous appearance of tan color to a cream-colored viscous smooth and homogeneous appearing emulsion. The number of stirring periods required to attain that result was reported under the test heading of Ease of Emulsification. I

In order to further improve the emulsion characteristics of the composition, particularly from the standpoint of ease of emulsification, there may be added to the composition in accordance with the present invention about 0.050.5% by weight of a linear isoolefinic' polymer having a molecular weight in excess of 2,000 and prefe ably in excess of 5,000. The manufacture of high molecular weight polymers of this type, such as from isobutylene, is well known as described in Otto et a1. Patent No. 2,084,501. These high molecular weight polymers are formed by condensation at low temperatures in the presence of a suitable catalyst such as BF3; and the higher molecular weight extremely viscous or solid products having a molecular weight from 10,000 to 20,000 or higher are conveniently employed. as a mineral lubricating oil solution or concentrate of the polymer. A very satisfactory material of this type for purposes of the present invention is the viscous stringy lubricating oil. concentrate containing about 50% by weight ofan isobutylene polymer having a molecular weight of around 20,000 which is manufactured by the Enjay Company under the name Paratac. In addition to improving the emulsion characteristics of the composition, this polymer additive also improves the adherence of the composition to the partsjbeing lubricated.

The followin Table II sets forth the results obtained on various compositions in the Emul- TABLE II Additive C0110. Per Cent Ease of Emulsificatipn- Stirring Periods 1 Per Cent 0 l Salt Sol.

Distilled Water BASE OII.--NAPHTHENE BASE LUBRIOATING OIL-S. U. S. AT

F or .BAS E OIL-NAPHTHENE BASE LUBRICATING OIL-S. U. S. AT

12.1-. 0.2 0.3 0.4 'r-o-so-so T-0-80-60 5 13"." 0.2 0.3 0.4 T-0-80-60 I08060 0 14...-.- 0.2 0.3 0.2 T-0-8060 'r-0-s0-00 15... 0.2 0.3

l Additive C-Lubricating oileoncentrate or about 50% by Weight of lsobutylene polymer of m. w x I I 9 Conventional 20%- blown rapeseed'oilcom about 20,000 i 51011 Test at 180 F. as well as the Ease of Emulsification Test, wherein additives A and B are respectively the same as in Table I and additive C is a lubricating oil concentrate containing about by weight of isobutylene polymer of molecular weight around 20,000. In this table, the results under Emulsion Test are reported in four numbers, which signifyirom left to right the m1. of oil separated, the ml. of water separated, the ml. of emulsion remaining, and the time in minutes after stirring was stopped that the readings were taken.

As will be noted from sam les 1 and 2 of the foregoin table, the polymer additive alone is lacking under these conditions as evidenced by almost complete separation into oil and water phases just five minutes after stirring was terminated. Samples 3-5 show that the combination of the polymer additive with the partial ester of the hexahydric alcohol anhydride is also comparatively ineffective, since there is substantial water separation at the termination of the -minute test. On the other hand, the combination of the polymer additive with the glyoxalidine primary additive provides highly efiective emulsification, as illustrated by samples 6 and 7, and constitutes a very satisfactory composition for certain purposes. Samples 8-14 inclusive show that the combination of the three additives provides the superior emulsification characteristics which are necessary in a marine engine lubricant; and, in comparison with sample 15 wherein the polymer additive was omitted, show that the ease of emulsification is materially improved by the presence of the third polymer additive, as illustrated by the number of stirring periods in the Ease of Emulsification Test. In fact, the compositioncontaining the three additives in the proportions set forth shows improved ease of emulsification under the conditions of this test over the conventional blown rapeseed oil composition.

From the foregoing tables, it will be noted that satisfactory .compositions prepared in accordance with the present invention contain extremely low proportions of additive in comparison to the conventional blown rapeseed oil composition of 10-20% additive content. Consequently, in order to produce a'lubricating composition of similar grade or viscosity in accordance with the present invention, it is necessary to employ a heavier base oil. It has been found that, while the lubricating composition per se of the present invention employing the heavier base oil with the smaller proportion of additives may have a comparable viscosity to the conventional blown rapeseed oil product, nevertheless when the two are emulsified with water the resulting emulsions are materially .difierent in fluidity. Thus the present composition when in emulsion forming characteristics,

formed into a 1:1 emulsion with water-possesses a thicker consistency as measured by a Brookfield viscosimeter at 100 F. than a 1:]. water emulsion of the conventional blown rapeseed oil composition of comparable initial viscosity. It has been further found that the addition of about 01-05% by weight of refined wool grease or lanolin to the foregoing compositions of the present invention reduces the emulsion consistency thereof to values more in line with the emulsion viscosities of the conventional rapeseed oil product. This is illustrated in the .fol-

lowing Table III, where additives A, B and C O are the same as in Tables I and H and additive D is lanolin.

TABLE III Naphthene base oil (S. U. .S'. at 100 F. of .769)

Additive Cone Viscosity of 1-1 Emul- Emulsion l sion Centipoises at Test at A B G D 100 F. 180 F. l

1.- 0.2 as. 0.4;. 3,680 o-o-so-co 2. U. 2 0. 3 0. 2 0. 1 2,320 (Fill-*) 3 U. 2 0.3 0. 2 U. 5 I, 320 1-0-79-50 4 0.2 1... 0.2 0.2 0D80fi6 5 .1 0. HI? 0. 2 0. 2 2, 210 1-0-7950 6. 1, (300 43-80-60 I Additive D-Lanolln. 5 Conventional 20% blown rapeseed oil comp. As shown by sample -1 in comparison with sample 6 of the foregoing table, the emulsion viscosity of the present composition in the absence of added lanolin is materially higher than that of the conventional rapeseed oil composition of comparable non-emulsified viscosity. Samples 2-5 inclusive show the effect of the added lanolin in the present composition with respect to reduction in emulsion consistency. It is to be noted that the addition of the lanolin to the present composition does not detract from the emulsion characteristics thereof as shown by the Emulsion Test at 180 F. In addition to the emulsion viscosity thinning effect, the lanolin also adds eiliness and a smoothing effect to the oil composition and to the water emulsion formed therefrom. I

Very satisfactory compositions for purposes of the present invention are represented by samples 2,'3 and5 of Table III although products represented by samples 1 and 4 are well suited to other uses. Complete tests on samples 4 and '5 are set forth by way of example in the following Table IV:

TABLE IV Tests on Compositions 4 and 5 of Table III Tests Comp. 4 Comp. 5

Gravity API 21. 2 21. 2 Flash, 0. Cleve, F 410 400 Fire, Glcva, Fun 455 470 Visc., S. U. at F 802 797 vise a U. at F 293 299 Visa, S. U. at 210 '1" 64 (i-i Viscosity index 30.8 31. 7 Color, 5 Love. Cell 115 110 Four, F -15 -l5 Corn, Cu Strip, 1 Neg Neg. Ash, Per Cent 0.007 0. 005 Emulsion Test at 180 F.:

Distilled Water 00-80-60 1-0-79-00 1% Salt Solution 10 0-70-60 l-0-79-60 Ease of Emulsification:

Stirring Periods at 75 F 3 3 Emulsion Stability16 hours at room temperature:

Distilled Water 5-0-75 4-0-76 1% Salt Solution 28-0-52 9-0-71 The foregoing table again illustrates the synergistic effect of the sorbitan mono-oleate in combination with other additives in repressing oil separation from the emulsion. This is shown by the Emulsion Test at 180 F. in the presence of 1% salt solution, and also by the Emulsion Stability Test. It is to be noted that both compositions show excellent results by the above described Ease of Emulsification test.

While composition 5 of Tables III and IV provided excellent lubrication in full scale marine engine tests, it did not emulsify as readily in the eccentric pans as conventional 20% blown rapeseed compositions, although the emulsion characteristics were entirely satisfactory on the smaller bearing surfaces on other parts of the engine such as links and connecting rods. A new test was therefore developed duplicating in miniature the motion of the engine eccentrics encountered on ships. For this purpose, a motor driven horizontal shaft equipped with a 4" diameter eccentric (eccentricity of '1 in.) was maintained with the eccentric dipping within a semi-circular pan (3%" radius x 2% wide) so that the eccentric at the extreme limit of its movement was about /2" from the semi-circular side of the pan. 250 milliliters of water and 250 milliliters of the oil composition under test were added to the pan, thereby bringing the level of the oil-water mixture to about 1" below the shaft axis. With this oil-water mixture maintained at 95-l00 F'., the shaft and cocentric were rotated at 125/R. P. M.; and the time in minutes for effecting complete emulsification of the mixture as determined visually in the manner described above was recorded. This test termed the Eccentric Emulsification Test was found to correlate well with actual service.

To further improve the ease of emulsification of the lubricant compositions of the present invention, as determined by the Eccentric Emulsification Test, the addition of about ODS-0.4%

by weight of a saturated fatty acid ester of an alkylolamine, where the saturated fatt acid contains to carbon atoms in the molecu e, is made in accordance with the present invention. Any one of the mono-, di-, and tri-alkylolamines, wherein the alkalolamine is combined with a soap-forming saturated fatty acid, can be employed. Other types of carboxyic ac ds, such as naphthenic acids and unsaturated fatty acids, are excluded. Examples of suitable materia's of this type include triethanolamine stearate, diethanolamine palmitate, tripropanolamine behenate, diethyl ethanolamine stearate and triethanolamine myristate. A preferred material for this purpose from the standpoint of availability is triethanolamine stearate, and this is listed in the followin tables by way of illustration.

Table V illustrates the results obtained in the above-described Eccentric Emulsification Test on compositions prepared in accordance with the present invention in comparison with the conventional rapeseed oil product.

TABLE V Eccentric Emulsification Test-,- Time in min.

Composition 1 Conventional 20% blown rapeseed oil 18, 14,11.

comp.

II Comp. 5+0.05% TEAS 45+.

1 'lriethanolamine stearate.

Samples 1 and 2 of the foregoing table show that the preferred composition 5 of Tables III and IV requires approximately 4-5 times as long to com- Test as does the conventional rapeseed oil composition. On the other'hand, samples 3-8 inclusive show that the presence of the small pro portion of added triethanolamine stearate, either as a partial replacement for the glyoxalidine additive or as a further additive to the composition, materially reduces the emulsification time by this test and renders the product at least equal if not superior to the conventional blown rapeseed oil composition with respect to ease of emulsification. While the saturated fatty acid esters of the alkylolamines have been found efiective for this purpose, the unsaturated fatty acid esters and the naphthenic acid esters are substantially ineffective. For example, the addition of from 0.1 to 0.2% triethanolamine oleate and from 0.1 to 0.2% triethanolamine naphthenate to the said composition 5 (also containing 1% sulfurized lard oil) gave times of 71-90 min. and min. respectively in the said Eccentric Emulsification Test. A proportion of around 0.1-0.2% of triethanolamine stearate in the composition is preferred for optimum overall results, since this material is not very soluble in mineral oil and higher proportions may result in some gel formation in the composition on storage at low temperatures of the order of 25-35 F. I V 7 Finally, in accordance with the presentinvention, the film strength and extreme pressure properties of the foregoing compositions may be improved by the addition of a sulfurized vegetable or animal oil wherein the sulfur is in a combined non-corrosive form so as to give a negative or non-corrosive result in the Copper Strip Corrosion Test at F. Any of the'varh ous animal and vegetable oils which are sulfurized at elevated temperatures and then blown with steam to remove HQS and render them noncorrosive, can be employed for this purpose, since these materials are found compatible with the other additives and do not interfere with or detract from the emulsifying properties of the composition. Examples of suitable sulfurized oils of this type for the present purpose are sulfurized lard oil, sulfurized rapeseed oil, sulfurized sperm oil, sulfurized cottonseed oil, and sulfurized palm oil. The sulfurized oil should be employed in the composition in a portion range of about 0.3-3.0% by weight and preferably about 0.5-1.5%.

A very satisfactory additive of this type which is prepared from a readily available material is sulfurized lard oil which was manufactured as follows: mixed with 10% by weight of powdered sulfur and the mixture raised to a temperature of 400 F. in eight hours with continuous stirring. The mixture was then held at this temperature for an additional three hours with intermittent stirring, and then blown with live steam for at least two hours to remove HzS. The product was allowed to cool to 250 F. with stirring and then drawn through a filter. The resulting sulfurized lard oil contains from about 6 to 10% of combined sulfur, generally around 7.5%, and is negative in the Copper Dish Corrosion Test at 100 F. A desirable characteristic of these sulfurized oils containing combined sulfur is that, while they are non-corrosive at lower temperatures, they have the ability to release sulfur at eX- ceptionally high temperature which may be occasionally encountered in service. The sulfurized 90% by weight of No. 1 lard oil was 11 lard oil per se gives a positive test in the Copper Strip Corrosion Test at 212 F. However, the lubricating composition of the present invention contains such a small proportion of the sul- 12 dine additive with other combinations of the foregoing described supplementary additives. For example the glyoxalidine additive may be used in combinationwith only the alkylolamine ester additive, where the emphasis is on case of emulsifurized oil that the composition passes the Cop- 5 per Strip Corrosion Test at 212 F. fication by the Eccentric Emulsification Test as Results obtained on a typical composition of opposed to stability of the emulsion. The inventhe present invention with the addition of typical tion also includes the foregoing composition consulfurized oils, demonstrating the improvement taining as a third additive either the partial hexiin extreme pressureproperties, are set forth in 1G tol anhydride ester to provide improved stability the following Table VI. The tests employed against oil separation, or the iso-olefinic polymer include the standard SAE and Timken extreme to provide improved adherence and still better allpressure tests for lubricants which are well around emulsion characteristics. A preferred known. In addition, the table gives the results composition for purposes of the present invention of a so-called modified southern Pacific Bearand possessing excellent overall emulsion charing Temperature Rise Test, which consists of acteristicsis the following: gradually loading a brass bearing on a rotating Per cent bushing until the bearing temperature reaches v by weight 250 F. The pressure on the bearing in pounds Mineral lubricating oil 94.2 -99.75 per sq. inch which is required to raise the bear- 2o l-hydroxy alkyl 2-010 to C30 alkenyl ing temperature to 250 F. is reported. Inasglyoxalidine 0.05- 0.4 much as the Timken and SAE tests encounter Alkylolamine Cit-C30 saturated fatty extremely high skin temperatures far above those acid ester 0.05- 0.4 encountered in marine lubrication, the Southern Hexahydric alcohol anhy Pacific test is thought to give a more practical gr; fatty acid partial ester 0.1 1.0 measure of the performance of marine lubri- Linear iso-olefinic poly er having cants. molecular weight over 5,000 0.05- 0.5

TABLE VI Mod S1. Bearing Temp.

1 Conv. 20% blown rapeseed oil. 85-110-95 15 20 1200, .1200 2 Comp. 5 of Ta eIII 110-10040 7 9 "70c, 100 3 Comp 5, 1% suliurized lard oil. 77-104-75 1200, 1200 4 Comp. 5, 1% sulfurizedrapseed oil 82-110-84 l0 l5 5 Comp. 5, 1% sulfurized sperm oil 128-106-128 10 15 ..Y.

As will be noted from the foregoing table, the To further improve the composition as listed test rated h Y Compositions BSSBII- immediately above with respect to emulsion contially the same within the accuracy of the test sistency, and to improve the oiliness f both HOWeVer! the Tlmimn and swthem oil and the emulsion, about 0.1 to'0.5% by weight Pacific tests show the conventional blown rapef1 dd d In dduo. seed oil composition to have better extreme pres- 0 mm m can 8 a e a 1 to e sure properties than composition 5 of Table III. extreme pressure properties and suppress 3 s m 3 of this table Shows that when 1% of formation, about 03-30% by weight of a nonsulfurized l w 11 prepared as described above corrosive sulfurized fatty oil extreme pressure was added to said composition 5, the extreme agent canbc add d. pressure properties of the resulting lubricant To further illustrate the present invention, the were essentially equalto the conventional blown following example i given of. a composition which i1 f 1f pomgosltlon y these Various testshas functioned very satisfactorily in actual service mines g g VII shows w lesults as a marine engine oil. The following Table VIII e Eccenti 1c Emulsification Test on the l preferred composition 5 of Table III when trisets forth the welght' and propqtmns of Ingram. ethanolamine stearate, and both the latter and ems employed to produce typlcal batch of thls sulfurjzed lard 011, are added. marine engine oil, together with tests on the in- TABLE VII dividual ingredients employed in producing the batch. Composition v 'IimeinMin. i TABLE VIII sunscreens:r 2 3 Comp. 5+O.l% TEAS 1 Ingredients Wt i l P 4 (SH-1% suliurized lard oi1 12 cent its indficiarted by this table, the ease of emulsificaf ggg fgg g a i l- 4 9 ion 0 e composition is not affected adversel e p a eceny by the addition of the sulfurized lard on, andig I iilttittiifi:::::::::::::::;:. 122i 3'. fact appears to be somewhat improved. %1921: 2353i fitnffiil iittof lsobu- 40.4 0.2 e p cific compositions described above are Triethanolamjnestearate 46.4 0.2 given by way Of example and the present Ewen. Salim-Zed lard on 232 ti on includes compositions composed 0f t base Total 23,196 -0 011 plus the specified proportions of the glyoxafi- 76, M

Tests on ingredients Tests on material used in batch Naphthene base lubricating oil:

Gravity, API 21.2

Flash -OCleve., F 415 Fire, Cleve. F

Visc., S. U. at 100 F 759 Visc., S. U. at 210 F 62.8

Color, Lovi. cell 120 Pour, F'

Neut. No

Ash, per cent 0.005

Corn, Cu. Strip, 3 hrs. at

212 F. l-hydroxyethyl 2 -heptadecenyl glyoxalidine Gravity, C./20 C 0.93'75 Visc., S. U. at 100 F 800 Visc., c. p. at 100 F 159 Color, ASTM 4.0

Emulsion test at 180 F.,

0.2% solution in naphthene base lubricating oil (S. U. at 100 F. of about 300) with distilled water 1-0-79-60 Sorbitan mono-oleate Sap. No 150 Hydroxyl No 221 Acid No 5.9 Visc., c. p. at C 1100 Sp. Gr 0.9923 Refined wool grease:

Color, NPA, diluted with water white kerosine 1.5

Melting point, F; Free fatty acid (as oleic),

per cent 0.14

Sap. No 94 Iodine No Water, per cent 0.2

Ash, per cent 0.05

Lube oil cone. of isobutylene polymer:

Appearance Viscous stringy pale colored liquid Triethanolamine stearate:

Color, FAC 1 Melting point, C 41.8

pH of 5% aqueous sol. at

25 C. 8.7 Gravity at 25/25 C 1.0229 Sulfurized lard oil:

Gravity, API 13.9

Visc., S. U. at 210 F 245 Sulfur, per cent 7.66

-Manufacture of any of the compositions previously described may be carried out by simple mixing of the ingredients in any suitable vessel at moderately warm temperatures. In the preparation of the foregoing batch, the mineral lubricating oil was charged to a steam heated kettle equipped with a mechanical stirrer. A small side mixer separate from the blending kettle was pref erably provided for incorporating the additives, with connections permitting the oil to be pumped from the large kettle up through the bottom of the side mixer, and permitting oil overflow from the side mixer to run back into the large kettle. This side mixer is particularly advantageous when a normally solid material of the character of the alkylolamine fatty acid ester is included in the batch.

After charging the oil to the large kettle, stirring was started and steam heat was turned on to raise the kettle and contents to a temperature of about -130 F. which was thereafter maintained in the manufacture of the batch. The side mixer was then started, utilizing a pumping rate of about 50 gallons or more per minute from the large kettle through the recirculating line to the side mixer and back to the kettle. The indicated amounts of the substituted glyoxalidine, the sorbitan mono-oleate, the refined wool grease and the isobutylene polymer concentrate were then added in order to the side kettle, with about 5-10 minutes being allowed for recirculation between the addition of each material.

At this point recirculation through the side mixer, which was full of the composition, was discontinued. The contents of the side mixer were then heated to F. with stirring. The indicated amount of triethanolamine stearate was added to the side mixer. Heating was continued to a temperature of about 210220 F. and this temperature was maintained for about 15 minutes to insure complete solution of the additive. Recirculation was then resumed. The concentrate was transferred to the main portion of the composition in the large kettle which meanwhile had been maintained at 120-130 F. The indicated amount of sulfurized lard oil was then added directly to the large kettle and stirring was continued for about hour until the'finished product was bright and clear. The final composition was then drawn to tankage.

Typical tests obtained on the foregoing composition, together with test specifications for'the product are set forth in the following Table Di:

TABLE IX fii g Specifications Gravity API 20. 9 18.0-22.0. Flash, O-Gleve., F 410 375 min.

Visa, S. U. at 100 F Emulsion Test VV-L-79ld Method Eccentric Emulsification Test 8, 11, 9, 10 30 max. Emulsion Stabi1ity0il separation 0 1 max.

after 2 hrs. at 180 F. in mi.

The Wick Feed Test of the foregoing table is U. S. Government Method 200.1, and is designed to indicate the manner in which the oil composition will feed through the wicks in marine engine service. This test employs a brass oil container of about 1 quart capacity fitted in the center with a brass tube of internal diameter serving as an oil-way and feeding into a graduated cylinder. A wick is employed which is composed of eight strands of worsted zephyr of the best quality, pure, long-fiber, cream White fine wool, thoroughly washed, scoured and carded, but not dyed or subjected to any chemical process. The strands are 4-ply soft spun and twisted; and the separate plies are of uniform thickness throughout their entire length. A wick support in the form of a hook of copper wire is employed which grips the outlet end of the wick below the level of the oil. The wick isdipped-inthe oil and placed in aposition with the oil container filled so that the lift ofthe wick is and this lift is maintained at from to /2" during the test. The flow of oil into the graduated cylinder is measured at the end of 24 and 48 hours and again at the end of la days. The Government specification requires that the flow at the end of 14 days shall be at least 30% of the flow during the initial periods of the test.

The foregoing Table IX also includes an Emul sion Stability Test which is more severe than the room temperature test previously described'and is employed in conjunction with the Eccentric Emulsification Test. After completion of the Eccentric Emulsification Test, 100 mls. of the emulsified mixture from the pan are transferred to a graduate and the latter is placed in a bath maintained at 180 F. After two hoursfin the bath, the number of mls. of separated oil and/or water are recorded.

While the invention has been described above particularly as a marine engine oil, it is to be understood that the invention is not limited to that service but is applicable to any lubricating service where water may be encountered and it is desired that a water-in-oil emulsion shall be produced in a manner to effectively remove the water from contact with the. metal parts and to maintain the latter coated with an adherent lubricating film. T

Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.

We claim:

1. A lubricating composition adapted to form a water-in-oil emulsion in the presence of water, with the water in the discontinuous phase, comprising a mineral lubricating oil as the predominant constituent, and constituting at least 90% by weight of the composition, and about 0.05- 0.4% by weight based on the composition of a substituted glyoxalidine having the formula where R is selected from the group consisting of hydrogen and lower alkyl, R is selected from the group consisting of alkyl' and alkenyl radicals having from to 30 carbon atoms, and X is selected from the group consisting of hydroxylower alkyl, amino-lower alkyl and amino-alky1- ene-imino-lower alkyl.

2. A lubricating composition according to claim 1, wherein R. is an alkenyl group having 15 to carbon atoms, and X is a hydroxy alkyl group.

3. A lubricating composition according to claim 2, wherein the substituted glyoxalidine is 1- hydroxyethyl Z-heptadecenyl glyoxalidine.

i. A lubricating composition adapted to form a water-in-oil emulsion in the presence of water, with the water in the discontinuous'phase, comprising a mineral lubricating oil as the predominant constituent, and constituting at least 90% by weight of the composition, about 0.054.492

16 by weight on the basisof the composition of a substituted glyoxalidine having the formula RCN where R- is selected from the group consisting of hydrogen and lower alkyl, R is selected from the group consisting of alkyl and alkenyl radicals having from 10 to 30 carbon atoms, and X is selected from the group consisting of hydroxylower alkyl, amino-lower alkyl and amino alkylene-imino-lower allryl. and about 0.1-1.0% by weight based on the composition of a higher fatty acid partial ester of a hexahydric alcohol anhydride, the fatty acid radical of said ester having from 10 to 30 carbon atoms.

5. A lubricating composition according to claim 4, wherein said ester is sorbitan mono-oleate.

6. A lubricating composition according to claim 5, wherein said glyoxalidine compound is lhydroxyethyl 2-hcptadecenyl glyoxalidine.

7. A lubricating composition adapted to form a water-in-oil emulsion in the presence of water, with the water in the discontinuous phase, comprising a mineral lubricating oil as the predominant constituent, and constituting at least by weight of the composition, about 0.05-0.4% by weight on the basis of the composition of a substituted glyoxalidine having the formula R Rats oa' R- -N/ l l a x where' R is selected from the group consisting of hydrogen and lower alkyl, R. is selected from the group consisting of alkyl and alkenyl radicals having from 10 to 30 carbon atoms, and X is selected from the group consisting of hydroxylower alkyl, amino-lower alkyl and amino-alkyleneimino-lower alkyl, and about ODS-0.4% by weight based on the composition of a saturated higher fatty acid ester of an alkylolainine where the saturated fatty acid contains 16 to 30 carbon atoms.

8. A lubricating composition according to claim 7, wherein the ester is a stearic acid ester.

9. A lubricating composition according to claim 8, wherein the ester is triethanolamine stearate.

10. A lubricating composition according to claim 7, wherein the composition also contains about (ll-1.0% by weight based on the composition of a higher fatty acid partial ester of a hexahydric alcohol anhydride, the fatty acid radical of said ester having from 10 to 30 carbon atoms.

11. A lubricating composition according to claim 10, wherein the partial ester is sorbitan mono-oleate.

12. A lubricating composition according to claim '7, wherein the composition also contains about 0.3-3.0% by weight based on the composition of a non-corrosive sulfurized fatty oil extreme pressure agent which is compatible with the said substituted giyoxalidine and the said ester and does not detract from the emulsification properties thereof.

13; A lubricating composition according to claim 12, wherein the said sulfurized fatty oil is sulfurized lard oil containing about -15% of combined sulfur.

14. A lubricating composition adapted to form a water-in-oil emulsion in the presence of water, with the water in the discontinuous phase, comprising a mineral lubricating oil as the predominant constituent and constituting at least 90% by weight of the composition, about 0.05-0.4% by weight on the basis of the composition of a substituted glyoxalidine having the formula R Rn :-N

\\CR R- N/ 4 where R is selected from the group consisting of hydrogen and lower alkyl, R is selected from the group consisting of alkyl and alkenyl radicals having from to 3-0 carbon atoms, and X is selected from the group consisting of hydroxylower alkyl, amino-lower alkyl and amino-alkylene-imino-lower alkyl, and about 0.05-0.5% by weight basedon the composition of a linear isoolefinic polymer having a molecular weight in excess of 2,000.

15. A lubricating composition according to claim 14, said composition also containing about 0.05-0.4% by weight based on the composition of a saturated fatty acid ester of an alkylolamine where the saturated fatty acid contains 10 to 30 carbon atoms, and about 0.1-0.5% by weight of lanolin.

16. A lubricating composition adapted to form a water-in-oil emulsion in the presence of water, with the water in the discontinuous phase, com prising the following ingredients in the listed proportions by weight based on the composition:

Per cent Mineral lubricating oil 94.2 -99.75 l-hydroxyalkyl 2-C1o-C30 alkenyl glyoxalidine 0.05- 0.4 Alkylolamine 016-030 saturated fatty acid ester 0.05- 0.4 Hexahydric alcohol anhydride C10- C30 fatty acid partial ester 0.1 1.0 Linear iso-olefinic polymer having molecular weight over 5000 0.05- 0.5

position:

Per cent Mineral lubricating oil 94.2 -99.75 l-hydroxyethyl 2-heptadecny1 glyoxalidine 0.05- 0.4 Triethanolamine stearate 0.05- 0.4 Sorbitan mono-oleate 0.1 1.0

Linear isobutylene polymer having molecular weight over 10,000 0.05- 0.5

Mineral lubricating oil 98.0

i 1 hydroxyethyl 2 4 heptadecenyl glyoxalidine 0.2 sorbitan 'mono-oleate 0.2 Lanolin 0.2 Triethanolamine stearate 0.2 Isobutylene polymer having molecular weight over 10,000 0.2 Sulfurized lard oil having about 6-10% of .21. A lubricating I composition according to claim 4 also containing about 0.05-0.5% by Weight based on the composition of a linear iso-olefinic polymer having a molecular weight in excess of 2,000.

22. A lubricating composition according to claim 21 also containing 0.3-3.0% by weight based on the composition of a non-corrosive sulfurized fatty oil extreme pressure agent which is compatible with said other additives and does not detract from the emulsification properties thereof.

.23. A marine engine oil adapted to form a water-in-oilemulsion in the presence of water, with the water in the discontinuous phase, com prising a mineral lubricating oil as the predominant constituent amounting to at least by weight of the compositiomabout 0.050.4% by weight based on the composition of l-hydroxyethyl Z-heptadecenyl glyoxalidine, about 0.1-1.-0% by weight of sorbitan mono-oleate, and about 0.05-0.5% by weight of a linear isobutylene polymer having a molecular weight in excess of 10,000.

24. A marine engine oil according to claim 23, also containing about 0.33.0% by weight based on the composition of sulfurized lard oil containing about 5-15% of combined sulfur, and about 0.1-0.5% by weight of lanolin.

ROY F. NELSON. ALTON J. DEUTSER. MELVIN R. HEF'IY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A LUBRICATING COMPOSITION ADAPTED TO FORM A WATER-IN-OIL EMULSION IN THE PRESENCE OF WATER, WITH THE WATER IN THE DISCONTINUOUS PHASE, COMPRISING A MINERAL LUBRICATING OIL AS THE PREDOMINANT CONSTITUENT, AND CONSTITUTING AT LEAST 90% BY WEIGHT OF THE COMPOSITION, AND ABOUT 0.050.4% BY WEIGHT BASED ON THE COMPOSITION OF A SUBSTITUTED GLYOXALIDINE HAVING THE FORMULA 